No-bake foundry mixes and their uses

ABSTRACT

This invention relates to polyurethane-forming foundry binder systems and foundry mixes which comprise a foundry aggregate, said foundry binder system, and a liquid amine curing catalyst. The binder system comprises a polyol component containing a polyether polyol and a monomeric glycol, and an organic polyisocyanate component. The foundry mixes are used to prepare foundry shapes made from foundry mixes by a no-bake process.

This application is a division of application Ser. No. 08/874,621, filedJun. 13, 1997, now U.S. Pat. No. 5,859,091.

FIELD OF THE INVENTION

This invention relates to polyurethane-forming foundry binder systemsand foundry mixes which comprise a foundry aggregate, said foundrybinder system, and a liquid amine curing catalyst. The binder systemcomprises a polyol component containing a polyether polyol and amonomeric polyol, and an organic polyisocyanate component. The foundrymixes are used to prepare foundry shapes made from foundry mixes by ano-bake process.

BACKGROUND OF THE INVENTION

In the foundry industry, one of the processes used for making metalparts is sand casting. In sand casting, disposable foundry shapes(usually characterized as molds and cores) are made by shaping andcuring a foundry mix which is a mixture of sand and an organic orinorganic binder.

One of the processes used in sand casting for making molds and cores isthe no-bake process. In this process, a foundry aggregate, binder, andliquid curing catalyst are mixed and compacted to produce a cured moldand/or core. In the no-bake process, it is important to formulate afoundry mix which will provide sufficient worktime to allow shaping.Worktime is the time between when mixing begins and when the mixture canno longer be effectively shaped to fill a mold or core.

A binder commonly used in the no-bake process is a polyurethane binderderived by curing a polyurethane-forming binder with a liquid tertiaryamine catalyst. Such polyurethane-forming binders used in the no-bakeprocess, have proven satisfactory for casting such metals as iron orsteel which are normally cast at temperatures exceeding about 1370° C.They are also useful in the casting of light-weight metals, such asaluminum, which have melting points of less than 815° C.

The polyurethane-forming binder usually consists of a phenolic resincomponent and polyisocyanate component which are mixed with sand priorto compacting and curing. Both the phenolic resin component andpolyisocyanate component generally contain a substantial amount oforganic solvent which can be obnoxious to smell and can create stressfor the environment such as smoke when the binder is cured. Because ofthis, there is an interest in developing binders which do not requirethe use of organic solvents.

U.S. Pat. No. 5,455,287 discloses no-bake foundry mixes where the bindercomprises (a) polyether polyol having a hydroxyl number between 200-600and a viscosity of 100-1000 centipoise at 25° C., (b) an organicpolyisocyanate component, and (c) a liquid tertiary amine catalyst,preferably a bicyclic tertiary amine.

SUMMARY OF THE INVENTION

This invention relates to a foundry mix comprising as a mixture:

(1) a foundry aggregate;

(2) a polyurethane binder comprising:

(a) a polyol component comprising:

(i) a polyether polyol; and

(ii) a monomeric polyol; and

(b) an organic polyisocyanate component;

(c) a catalytically effective amount of a liquid tertiary aminecatalyst, wherein components (a) and (b) are compatible with each other.

The invention also relates foundry binder systems used in the foundrymixes and to the use of these foundry mixes in a no-bake process forpreparing foundry shapes. Additionally, the invention also relates tothe use of these foundry shapes to cast metal parts.

The foundry binder has a lower viscosity than those utilized in U.S.Pat. No. 5,455,287 which allows for easier pumping (even in the winter)and mixing of the sand and binder, and improves the bonding between thesand and the binder. Comparison experiments show that immediate, 1 hour,and 3 hour tensiles strengths are improved by combining the polyetherpolyol and the monomeric polyol.

The binders of the foundry mixes are most preferably free of freeformaldehyde and free phenol. However, they may small amounts of freeformaldehyde, i.e. no more than 2 weight percent free formaldehyde,preferably no more than 1 percent, and no more than 2 weight percentfree phenol, preferably no more than 1 percent. Preferably, the bindersdo not contain solvents and thus are low in odor when mixing with sand,and do not produce much smoke during pour off which creates less stressto the environment than conventional polyurethane-forming binders. Thesand shakes out from the castings effectively and the surface finish ofthe casting is good.

BEST MODE AND OTHER MODES

The polyether polyols which are used in the polyurethane-forming foundrybinders are liquid polyether polyols or blends of liquid polyetherpolyols having a hydroxyl number of from about 200 to about 600,preferably about 300 to about 500 milligrams of KOH based upon one gramof polyether polyol. The viscosity of the polyether polyol is from 100to 1,000 centipoise, preferably from 200 to 700 centipoise, mostpreferably 300 to 500 centipoise. The polyether polyols may have primaryand/or secondary hydroxyl groups.

These polyols are commercially available and their method of preparationand determining their hydroxyl value is well known. The polyetherpolyols are prepared by reacting an alkylene oxide with a polyhydricalcohol in the presence of an appropriate catalyst such as sodiummethoxide according to methods well known in the art. Any suitablealkylene oxide or mixtures of alkylene oxides may be reacted with thepolyhydric alcohol to prepare the polyether polyols. The alkylene oxidesused to prepare the polyether polyols typically have from two to sixcarbon atoms. Representative examples include ethylene oxide, propyleneoxide, butylene oxide, amylene oxide, styrene oxide, or mixturesthereof. The polyhydric alcohols typically used to prepare the polyetherpolyols generally have a functionality greater than 2.0, preferably from2.5 to 5.0, most preferably from 2.5 to 4.5. Examples include ethyleneglycol, diethylene glycol, propylene glycol, trimethylol propane, andglycerine.

The monomeric polyols used in the polyol component have an averagefunctionality of 2 to 4, hydroxyl numbers from 500 to 2000, morepreferably from 700 to 1200, and viscosities less than 200 centipoise at25° C., preferably less than 100 centipoise at 25° C. Examples of suchmonomeric polyols include ethylene glycol, diethylene glycol,triethylene glycol, 1,3-propane diol, 1,4-butanediol, 1,2,4-butanetriol,dipropylene glycol, tripropylene glycol, glycerin, tetraethylene glycol,and mixtures thereof.

The weight ratio of the polyether polyol to the monomeric polyol in thepolyol component is from 70:30 to 30:70, preferably from 60:40 to 40:60.

Although not preferred, minor amounts of phenolic resin and/oramine-based polyols can be added to the polyether polyol. By minoramounts, it is meant that less than 15 weight percent, preferably lessthan 5 weight percent, said weight percent based upon the weight of thepolyether polyol component. If a phenolic resin is added to thepolyether polyol, the preferred phenolic resins used are benzylic etherphenolic resins which are specifically described in U.S. Pat. No.3,485,797 which is hereby incorporated by reference into thisdisclosure.

Although not preferred, organic solvents may be added to the polyolcomponent, particularly if a benzylic ether phenolic resin is used. Theamount of solvent used is generally less than 15 weight percent basedupon the total weight of the polyol component, preferably less that 5weight percent.

Other optional ingredients which may be added to the polyether includerelease agents and adhesion promoters, such as silanes described in U.S.Pat. No. 4,540,724 which is hereby incorporated into this disclosure byreference, to improve humidity resistance.

Organic polyisocyanates used in the organic polyisocyanate component areliquid polyisocyanates having a functionality of two or more, preferably2 to 5. They may be aliphatic, cycloaliphatic, aromatic, or a hybridpolyisocyanate. Mixtures of such polyisocyanates may be used. Thepolyisocyanates should have a viscosity of about 100 to about 1,000,preferably about 200 to about 600.

Representative examples of polyisocyanates which can be used arealiphatic polyisocyanates such as hexamethylene diisocyanate, alicyclicpolyisocyanates such as 4,4'-dicyclohexylmethane diisocyanate, andaromatic polyisocyanates such as 2,4- and 2,6-toluene diisocyanate,diphenylmethane diisocyanate, and dimethyl derivates thereof. Otherexamples of suitable polyisocyanates are 1,5-naphthalene diisocyanate,triphenylmethane triisocyanate, xylylene diisocyanate, and the methylderivates thereof, polymethylenepolyphenyl isocyanates,chlorophenylene-2,4-diisocyanate, and the like.

The polyisocyanates are used in sufficient concentrations to react withthe polyether polyol and cure in the presence of the liquid amine curingcatalyst. In general the isocyanate ratio of the polyisocyanate to thehydroxyl of the polyol component (NCO/OH ratio), is from 1.25:1.0 to0.60:1.0, preferably about 0.9:1.0 to 1.1:1.0, and most preferably about1.0:1:0.

The polyisocyanate component may contains a natural oil Representativeexamples of natural oils which are used in the isocyanate component arelinseed oil including refined linseed oil, epoxidized linseed oil,alkali refined linseed oil, soybean oil, cottonseed oil, RBD Canola oil,refined sunflower oil, tung oil, and dehydrated castor oil.

Optional ingredients such as release agents and solvents may also beused in the organic polyisocyanate component.

Although not preferred, solvents may be used in the organicpolyisocyanate component and/or polyol component. If solvents are usedin either, those skilled in the art will know how to select them.Typical organic solvents which are used include aromatic solvents,esters, or ethers, preferably mixtures of these solvents. Preferably,these solvents are used in amounts less than about preferably less than15 weight percent based upon the weight of the isocyanate component,more preferably less that 5 weight percent.

The binder is preferably made available as a three package system withthe polyol component in one package, the organic polyisocyanatecomponent in the second package, and the catalyst in the third package.When making foundry mixes, usually the binder components are combinedand then mixed with sand or a similar aggregate to form the foundry mixor the mix can be formed by sequentially mixing the components with theaggregate. Preferably the polyether polyol and catalyst are first mixedwith the sand before mixing the isocyanate component with the sand.Methods of distributing the binder on the aggregate particles arewell-known to those skilled in the art. The mix can, optionally, containother ingredients such as iron oxide, ground flax fibers, wood cereals,pitch, refractory flours, and the like.

The liquid amine catalyst is a base having a pK_(b) value generally inthe range of about 7 to about 11. The term "liquid amine" is meant toinclude amines which are liquid at ambient temperature or those in solidform which are dissolved in appropriate solvents. The pK_(b) value isthe negative logarithm of the dissociation constant of the base and is awell-known measure of the basicity of a basic material. The higher thisnumber is, the weaker the base. The bases falling within this range aregenerally organic compounds containing one or more nitrogen atoms.

Specific examples of bases which have pK_(b) values within the necessaryrange include 4-alkyl pyridines wherein the alkyl group has from one tofour carbon atoms, isoquinoline, arylpyridines such as phenyl pyridine,pyridine, acridine, 2-methoxypyridine, pyridazine, 3-chloro pyridine,quinoline, N-methyl imidazole, N-ethyl imidazole, 4,4'-dipyridine,4-phenylpropylpyridine, 1-methylbenzimidazole, and 1,4-thiazine.Preferably used as the liquid tertiary amine catalyst is an aliphatictertiary amine, particularly POLYCAT 9[tris(3-dimethylamino)propylamine)] catalyst sold by Air Products.

In view of the varying catalytic activity and varying catalytic effectdesired, catalyst concentrations will vary widely. In general, the lowerthe pK_(b) value is, the shorter will be the worktime of the compositionand the faster, more complete will be the cure. In general, catalystconcentrations will be a catalytically effective amount which generallywill range from about 0.2 to about 5.0 percent by weight of thepolyether polyol, preferably 1.0 percent by weight to 4.0 percent byweight, most preferably 2.0 percent by weight to 3.5 percent by weightbased upon the weight of the polyether polyol.

In a preferred embodiment of the invention, the catalyst level isadjusted to provide a worktime for the foundry mix of 3 minutes to 10minutes, preferably 8 minutes to about 10 minutes, and a striptime ofabout 4 minutes to 12 minutes, preferably 9 minutes to about 10 minutes.Worktime is defined as the time interval after mixing thepolyisocyanate, polyether, and catalyst and the time when the foundryshape reaches a level of 60 on the Green Hardness "B" Scale Gauge soldby Harry W. Dietert Co., Detroit, Mich. Striptime is time interval aftermixing the polyisocyanate, polyether, and catalyst and the time when thefoundry shape reaches a level of 90 on the Green Hardness "B" ScaleGauge.

In this preferred embodiment, the ratio of the isocyanate groups of thepolyisocyanate to hydroxyl groups of the polyol is preferably about0.9:1.0 to about 1.1:1.0, most preferably about 1.0:1:0, the hydroxylnumber of the polyol is from about 200 to about 500, and the weightratio of polyisocyanate to polyether polyol is from about 65:35 to about35:65, preferably about 45:55. These parameters provide optimumworktime, striptime, and tensile properties.

Various types of aggregate and amounts of binder are used to preparefoundry mixes by methods well known in the art. Ordinary shapes, shapesfor precision casting, and refractory shapes can be prepared by usingthe binder systems and proper aggregate. The amount of binder and thetype of aggregate used is known to those skilled in the art. Thepreferred aggregate employed for preparing foundry mixes is sand whereinat least about 70 weight percent, and preferably at least about 85weight percent, of the sand is silica. Other suitable aggregatematerials for ordinary foundry shapes include zircon, olivine,aluminosilicate, chromite sand, and the like.

In ordinary sand type foundry applications, the amount of binder isgenerally no greater than about 10% by weight and frequently within therange of about 0.5% to about 7% by weight based upon the weight of theaggregate. Most often, the binder content for ordinary sand foundryshapes ranges from about 0.6% to about 5% by weight based upon theweight of the aggregate in ordinary sand-type foundry shapes.

The aggregate employed with the catalyzed binder in producing thefoundry mix should be sufficiently dry so that a handleable foundryshape results after a worktime of 3 to 10 minutes and a strip time of 4to 12 minutes. Generally the amounts of moisture in the aggregate isless than about 0.5 per cent by weight, preferably less than about 0.2percent by weight, and most preferably less than about 0.1 percent byweight based on the weight of the sand.

EXAMPLES

The examples which follow will illustrate specific embodiments of theinvention. These examples along with the written description will enableone skilled in the art to practice the invention. It is contemplatedthat many other embodiments of the invention will be operable besidesthose specifically disclosed.

In all of the examples, the test specimens, unless otherwise indicated,were produced by the no-bake process using 3.5 weight percent, based onthe Part I, of POLYCAT 9 catalyst sold by Air Products which is 12.5weight percent tris(3-dimethylamino)propylamine in dipropylene glycol.All parts are by weight and all temperatures are in °C. unless otherwisespecified.

Unless otherwise indicated, the foundry mixes were prepared by firstmixing 4000 parts WEDRON 540 sand with the polyol component and thecatalyst for about 2 minutes. Then the MONDUR MR was mixed with themixture of sand, polyol component, and catalyst for about 2 minutes. Thecomposition of the polyol component and the binder level, whereappropriate, is specified in Tables I and II. The amount of polyolcomponent and polyisocyanate was such that the ratio of hydroxyl groupsof the polyol component to isocyanato groups of the polyisocyanate wasabout 1:1 and the weight ratio of polyol to polyisocyanate was about41:59.

Measuring the tensile strength of the dog bone shapes enables one topredict how the mixture of sand and binder will work in actual foundryoperations. The foundry shapes were stored 0.5 hour, 1 hour, 3 hours and24 hours in a constant temperature room at a relative humidity of 50%and a temperature of 25° C. before measuring their tensile strengths.Unless otherwise specified, the tensile strengths were also measured onshapes stored 24 hours at a relative humidity (RH) of 100%.

The following terms were used in the examples:

    ______________________________________                                        BOS          =     based on sand.                                               DEG = diethylene glycol having OH # of                                          1058, functionality of 2 and viscosity of                                     28 cps.                                                                     DPG = dipropylene glycol.                                                     MONDUR MR = an organic polyisocyanate commercially                              available from BAYER AG having a                                              functionality of 2.5 to 2.7.                                                PEP = polyether polyol.                                                       PLURACOL POLYOL                                                               TP-440 = a polyether polyol, sold commercially by                               BASF, having an OH value of 398, pre-                                         pared by reacting propylene oxide with                                        trimethylol propane.                                                        RH = relative humidity.                                                       ST = striptime.                                                               TEG = triethylene glycol having an OH # of                                      748, a functionality 2, and a viscosity                                       of 35 cps.                                                                  VIS = viscosity.                                                              WT = worktime.                                                              ______________________________________                                    

Control A and B and Example 1

Control A is based upon the teachings of U.S. Pat. No. 5,455,287 anddoes not contain a glycol while Control B uses a glycol, trethyleneglycol, but does not use a polyether polyol. Table I shows the resultsof Control A and B compared to the formulations of Example 1 where amixture of a polyether polyol and were used as the polyol component at abinder level of 1.3 weight percent based upon the weight of the sand.

                  TABLE I                                                         ______________________________________                                        TENSILE PROPERTIES OF CORES                                                                  VIS              TENSILE (PSI)                                 EXAMPLE PEP    TEG     (cps)                                                                              WT/ST   30'  1 HR 3 HR                            ______________________________________                                        Control A                                                                             100     0      632  13.25/23.00                                                                           100  254  302                               Control B  0 100  35 6.25/11.50  15  27  45                                   1  50  50 100 4.25/7.50 257 322 353                                         ______________________________________                                    

The data in Table I indicate that the foundry binder binders containingthe mixture of polyether polyol and glycol have lower viscosities andimproved tensile strengths even though they are solventless. This resultis surprising in view of the low tensile strengths that result whentriethylene glycol is used alone. Such binders are clearly moreenvironmentally friendly and create less odor and smoke.

Example 2

Example 2 was essentially repeated except diethylene glycol was used asthe glycol instead of triethylene glycol. The binder consisted ofpolyether polyol TP-440 and diethylene glycol at 60/40 blend. Table IIshows this binder performed well in sand tensile strength developmenttoo.

                  TABLE II                                                        ______________________________________                                        TENSILE PROPERTIES OF CORES                                                                  VIS             TENSILE (PSI)                                  EXAMPLE PEP     DEG    (cps) WT/ST 30'  1 HR  3 HR                            ______________________________________                                        2       60      40     83    3.3/5.8                                                                             105  152   176                             ______________________________________                                    

Examples 3-5

Examples 3-5 show the effect of changing the binder level in theformulations containing the polyether polyol and the glycol. In theseexamples, triethylene glycol was used as a 50/50 blend with thepolyether polyol. Table III shows that reducing binder levels from 1.5to 1.0% resulted in minor decreases of the sand tensile strengths aswell as an increase of the WT/ST).

                  TABLE III                                                       ______________________________________                                        TENSILE PROPERTIES OF CORES AT                                                  VARYING BINDER LEVELS                                                                            TENSILE (PSI)                                            EX-                                            24 HR                            AM- BINDER VIS     24 100%                                                    PLE LEVEL (cps) WT/ST 30 1 HR 3 HR HR RH                                    ______________________________________                                        3    1.5      100    3.5/5.5                                                                             282  278  321  317  40                               4  1.25 100 4.3/7.5 224 270 318 307 41                                        5 1.0 100 5.5/10.2 148 207 225 287 40                                       ______________________________________                                    

The data in Examples 3-5 indicate that worktime/striptime increases withdecreasing binder level and the tensile strengths of the test specimensincrease with increasing binder level.

We claim:
 1. A no-bake foundry mix comprising in admixture:a foundryaggregate: a binder comprising:(1) a polyol component comprising(a) apolyether polyol; and (b) a monomeric polyol having a hydroxyl number of700 to 1,200; (2) an organic polyisocyanate component, wherein theweight ratio of polyether polyol to monomeric polyol in the polyolcomponent is from 70:30 to 30:70 and the polyol component contains lessthan 15 weight percent of phenolic resin; and C. a catalyticallyeffective amount of a liquid tertiary amine catalyst.
 2. The foundry mixof claim 1 wherein the monomeric monomeric polyol has a hydroxylfunctionality of from about 2.0 to about 4.0, and a viscosity of lessthan 100 centipoise at 25° C.
 3. The foundry mix of claim 2 wherein themonomeric polyol is selected from the group consisting of ethyleneglycol, diethylene glycol, triethylene glycol, 1,3-propane diol,1,4-butanediol, 1,2,4-butane triol, dipropylene glycol, tripropyleneglycol, and mixtures thereof.
 4. The foundry mix of claim 3 wherein thetertiary amine catalyst is an aliphatic tertiary amine.
 5. The foundrymix of claim 4 wherein the amount of moisture in the aggregate is lessthan about 0.1 weight percent based upon the total weight of theaggregate.
 6. The foundry mix of claim 5 wherein the tertiary aminecatalyst is tris(3-dimethylamino)propylamine.
 7. A process for casting alow melting metal which comprises:A. fabricating a foundry shape by theno-bake process wherein said shape is prepared with a foundry mix ofclaim 1; B. pouring said low melting metal while in the liquid stateinto and around said shape; C. allowing said low melting metal to cooland solidify; and D. then separating the molded article.
 8. A metalcasting prepared in accordance with claim
 7. 9. A no-bake foundry bindersystem comprising as separate components:A. a polyol componentcomprising(a) a polyether polyol; and (b) a monomeric polyol having ahydroxyl number of 700 to 1,200; B. an organic polyisocyanate component,wherein the weight ratio of polyether polyol to monomeric polyol in thepolyol component is from 70:30 to 30:70 and the polyol componentcontains less than 15 weight percent of phenolic resin; and C. acatalytically effective amount of a liquid tertiary amine catalyst. 10.The binder system of claim 9 wherein the monomeric glycol has a hydroxylfunctionality of from about 2.0 to about 4.0, and a viscosity of lessthan 100 centipoise at 25° C.
 11. The binder system mix of claim 10wherein the monomeric polyol is selected from the group consisting ofethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, and 1,4-butanediol, 1,2,4-butanetriol, dipropylene glycol,tripropylene glycol, and mixtures thereof.
 12. The binder system ofclaim 11 wherein the tertiary amine catalyst is an aliphatic tertiaryamine.
 13. The binder system of claim 12 wherein the amount of moisturein the aggregate is less than about 0.1 weight percent based upon thetotal weight of the aggregate.
 14. The binder system of claim 13 whereinthe tertiary amine catalyst is tris(3-dimethylamino)propylamine.